The present invention is a process for converting a high-boiling fraction, resulting from the reaction of methyl chloride with silicon metalloid in a process typically referred to as the "direct process", to monosilanes. The process comprises forming a mixture comprising a low-boiling fraction comprising monosilanes and a high-boiling fraction comprising polymeric silicon containing compounds and contacting the mixture with hydrogen gas in the presence of a catalyst effective in promoting conversion of the polymeric silicon containing compounds to monosilanes. The present process results in conversion of the high-boiling fraction to monosilanes. At least a portion of the catalyst required for conduct of the process may be formed in situ during conduct of the direct process and isolation of the fractions.
In the preparation of methyl chlorosilanes by the direct process a complex mixture is formed which is typically distilled to separate methylchlorosilanes from other components present in the mixture. After the methylchlorosilanes are distilled from the mixture, remaining are monosilane and disilane by-product fractions. The monosilane fraction which boils below about 45.degree. C. is hereinafter referred to as "low-boiling fraction" and the disilane fraction which boils above about 80.degree. C. is hereinafter referred to as "high-boiling fraction." In current commercial operations for performing the direct process, the high-boiling fraction alone can constitute as much as five weight percent of the resultant product. Therefore, it is desirable to convert the high-boiling fraction along with the low-boiling fraction into commercially desirable products to reduce by-product disposal and to improve raw material utilization.
The "direct process" is well described in the patent literature, for example, in Rochow, U.S. Pat. No. 2,380,995 and Barry et al., U.S. Pat. No. 2,488,487. The high-boiling fraction remaining after the monosilanes overhead distillation is a complex mixture comprising higher boiling silicon containing compounds which have, for example, SiSi, SiOSi, and SiCSi linkages in the molecules. The high-boiling fraction may also contain particulate silicon and metals or compounds thereof. Typical high-boiling residues obtained from the direct process distillation product are described, for example, in Mohler et al., U.S. Pat. No. 2,598,435 and Barry et al., U.S. Pat. No. 2,681,355.
Wagner, U.S. Pat. No. 2,606,811, teaches a hydrogenation process where a compound containing a halogen and the Si--Si bond is heated to a temperature of at least 300.degree. C. in the presence of hydrogen. The resultant products are monosilanes.
Atwell et al., U.S. Pat. No. 3,639,105, describe a process where hydrosilanes are produced by contacting a disilane with hydrogen gas under pressure and heating the mixture in the presence of a transition metal catalyst such as palladium on charcoal. Atwell et al. state that the disilane may be part of a mixture from the direct process. Atwell et al. further report that when the disilane was a methylchlorodisilane, the resulting product contained about four to 28 weight percent methyltrichlorosilane. Generally, organotrihalosilanes such as methyltrichlorosilane have limited commercial usefulness and for this reason limit the usefulness of the process described by Atwell et al.
Neale, U.S. Pat. No. 4,079,071, describes a process for preparing hydrosilanes in high yields by reacting methylchloropolysilanes with hydrogen gas under pressure at a temperature of from 25.degree. C. to about 350.degree. C. in the presence of a copper catalyst. Neale states that the methylchloropolysilanes can be those typically created as direct process by-products. Useful copper catalysts described by Neale include copper metal, copper salts, and complexes of copper salts with organic ligands. In some cases, Neale reports that up to 29 weight percent methyltrichlorosilane was formed.
Ritzer et al., U.S. Pat. No. 4,393,229, describe a process for converting alkyl-rich disilanes in a residue obtained from the manufacture of alkylhalosilanes to halogen-rich polysilanes. The process comprises treating an alkyl-rich disilane-containing residue with an alkyltrihalosilane or silicon tetrahalide in the presence of a catalyst and a catalytic amount of a hydrosilane reaction promoter at an elevated temperature. Ritzer et al. teach aluminum trichloride as a useful catalyst in their process when used with a hydrosilane promoter. Ritzer et al. further teach that the resulting halogen-rich polysilanes can, in a separate step, be cleaved to form monosilanes.
Bokerman et al., U.S. Pat. No. 5,175,329, describe a process for the production of organosilanes from the high-boiling residue resulting from the direct process that results in a net consumption of organotrichlorosilane. In the process, the high-boiling residue is contacted with an organotrichlorosilane and hydrogen gas in the presence of both a hydrogenation catalyst and a redistribution catalyst.
Ferguson et al., U.S. Pat. No. 5,430,168, describe a process for the production of monosilanes from the high-boiling residue resulting from the "direct process." The process comprises forming a mixture comprising an organotrihalosilane and high-boiling residue in the presence of hydrogen gas and a catalytic amount of aluminum trichloride. The process results in consumption of the organotrihalosilane and conversion of the high-boiling residue to useful monosilanes.
The present invention provides a process where a high-boiling fraction comprising polymeric silicon containing compounds resulting from producing methyl chlorosilanes is converted into commercially useful monosilanes. The present inventors have discovered that by forming a mixture comprising a low-boiling distillation fraction comprising monosilanes resulting from the reaction of methyl chloride with silicon metalloid and a high-boiling distillation fraction comprising polymeric silicon containing compounds, that the high-boiling fraction is converted to useful monosilanes. Furthermore, at least a portion of the catalyst in the present process can be formed in situ during conduct of the direct process and isolation of the resulting monosilanes.